Dimerized thiourea derivatives, near-infrared absorbents comprising the same, and heat wave shielding materials comprising the same

Abstract: A composition which comprises a thiourea derivative of Formula [1] or [2]: and a copper compound, may be used to prepare a near-infrared resin material which has a wide absorption in the near-infrared region. Typical examples of the dimerized thiourea derivative are 4,4'-di(benzylthiocarbamoyl)-aminodiphenylmethane, 4,4'-di(benzylthiocarbamoyl)-aminodiphenylhexafluoropropane, and 1,4'-di(dibenzoylthiocarbamoylamino)-2,5-dimethylbenzene and typical examples of the copper compound are copper stearate and copper β-acryloyloxypropylhydrogenphthalate.

Description: This invention relates to a novel dimerized thiourea derivative, a near-infrared absorbent composition comprising the dimerized thiourea derivative and a copper compound, a near-infrared absorbent obtained by heating the composition, a near-infrared absorbent resin obtained by melting the near-infrared absorbent composition or the near-infrared absorbent, and a heat wave shielding material using the near-infrared absorbent resin. In EP-A-0 346 772 (based on Japanese patent applications 145262/88 and 232075/88, laid open as Japanese OPI 2-3493 and 2-80486, respectively,) and in Japanese Patent Laid-open Publications (Japanese OPI) 2-34682 and 3-246256, the inventors already disclosed a near-infrared absorbent composition comprising a thiourea compound and a copper compound, a near-infrared absorbent material obtained by heating the composition, and a near-infrared absorbent resin molding containing the absorbents in a resin, or a near-infrared absorbent resin molding obtained by mixing the absorbents with a radical polymerization initiator and heating the mixture to polymerize. These near-infrared absorbents obtained by heating a composition comprising a thiourea compound and a copper compound are inexpensive compared to near-infrared absorbent dyes known in the past, and superior in terms of light fastness and near-infrared absorption range. However, when containing a composition comprising a prior art thiourea compound and a copper compound in a resin and molding to a pellet or a specified form, the composition tends to undergo partial decomposition due to the molding heat, resulting in gas evolution. Therefore, a primary object of the present invention is to provide a near-infrared absorbent composition, and a near infrared absorbent, which, heat molded to produce a near-infrared absorbent resin, do not decompose or generate malodorous gases at the molding temperature, a near-infrared absorbent resin containing these near-infrared absorbent composition and near-infrared absorbent, and a heat wave shielding material comprising the resin. The above object is attained by a thiourea compound (hereinafter referred to as "dimerized thiourea compound") which has two thiourea structures (-NH-(C=S)-NH-) in the molecule. In accordance with the present invention, there is provided a composition comprising a copper compound and a dimerized thiourea compound of Formula [1]: wherein A denotes CH 2 , (CH 2 ) 2 , S, O, SO 2 , CONH, NH, or C(CF 3 ) 2 ; the two substituents R, which may be the same or different, are each independently selected from a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 18carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms; and each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , which may be the same or different, is independently selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a halogen and hydrogen; the molar ratio of dimerised thiourea derivative to copper compound being from 8:2 to 1:2. The invention further provides a composition comprising a copper compound and a dimerised thiourea derivative of Formula [2]: wherein the two substituents R, which may be the same or different, are each independently as defined above for R in Formula [1]; and B denotes substituted or unsubstituted benzene ring, napthalene ring, or a biphenyl ring; the molar ratio of dimerised thiourea derivative to copper compound being from 8:2 to 1:2. In R of Formula [1] and Formula [2], the alkyl group includes, for instance, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, heptyl, dodecyl and stearyl; the cycloalkyl group includes, for instance, cyclohexyl; the aralkyl group includes, for instance, benzyl and p-phenylethyl; the aryl group includes, for instance, phenyl, chlorophenylgroup, fluorophenyl, toluyl, cyanophenyl, nitrophenyl, methoxyphenyl and 1-naphthyl; the acyl group includes, for instance, benzoyl; the alkenyl group includes, for instance, allyl, 2-butenyl and 4-pentenyl; and the alkoxycarbonyl group includes, for instance, ethoxycarbonyl. Examples of the dimerized thiourea derivative of Formula [1] used in the present invention include, but are not limited to, the following: 4,4' -di(phenylthiocarbamoylamino)diphenylmethane, 4,4'-di(benzylthiocarbamoylamino)diphenylmethane, 4,4'-di(benzoylthiocarbamoylamino)diphenylmethane, 4,4'-di(ethylthiocarbamoylamino)diphenylmethane, 4,4'-di(n-butylthiocarbamoylamino)diphenylmethane, 4,4'-di(allylthiocarbamoylamino)diphenylmethane, 4,4'-di(ethoxycarbonylthiocarbamoylamino)diphenylmethane, 4,4'-di(phenylthiocarbamoylamino)diphenylether, 4,4'-di(p-tolylthiocarbamoylamino)diphenylether, 4,4'-di(tert-butylthiocarbamoylamino)diphenylether, 4,4'-di(benzylthiocarbamoylamino)diphenylether, 4,4'-di(benzoylthiocarbamoylamino)diphenylether, 4,4'-di(phenylthiocarbamoylamino)diphenylsulfone, 4,4'-di(p-chlorophenylthiocarbamoylamino)diphenylsulfone, 4,4'-di(iso-butylbenzylthiocarbamoylamino)diphenylsulfone, 4,4'-di(benzylthiocarbamoylamino)diphenylsulfone, 4,4'-di(benzoylthiocarbamoylamino)diphenylsulfone, 4,4'-di(phenylthiocarbamoylamino)diphenylsulfide, 4,4'-di(o-tolylthiocarbamoylamino)diphenylsulfide, 4,4'-di(dodecylthiocarbamoylamino)diphenylsulfide, 4,4'-di(benzylthiocarbamoylamino)diphenylsulfide, 4,4'-di(phenylthiocarboylamino)benzanilide, 4,4'-di(cyclohexylthiocarbamoylamino)benzanilide, 4,4'-di(benzylthiocarbamoylamino)benzanilide, 4,4'-di(phenylthiocarbamoylamino)diphenylethane, 4,4'-di(m-tolylthiocarbamoylamino)diphenylethane, 4,4'-di(octadecylthiocarbamoylamino)diphenylethane, 4,4'-di(benzylthiocarbamoylamino)diphenylethane, 4,4'-di(diphenylthiocarbamoylamino)-3,3'-dimethyldiphenylmethane, 4,4'-di(p-methoxyphenylthiocarbamoylamino)-3,3'-dimethyldiphenylmethane, 4,4'-di(benzylthiocarbamoylamino)-3,3'-dimethyldiphenylmethane, 4,4'-di(benzoylthiocarbamoylamino)-3,3'-dimethyldiphenylmethane, 4,4'-di(benzylthiocarbamoylamino)diphenylamine, 4,4'-di(benzylthiocarbamoylamino)diphenylamine, 4,4'-di(benzoylthiocarbamoylamino)diphenylamine, 4,4',-di(benzylthiocarbamoylamino)diphenylfluoropropane, and 4,4'-di(benzoylthiocarbamoylamino)diphenylhexafluoropropane. Further, examples of the dimerized thiourea derivative of Formula [2] used in the present invention include, but are not limited to, the following: 1,3-di(benzylthiocarbamoylamino)benzene, 1,3-di(benzoylthiocarbamoylamino)-2-methylbenzene, 1,3-di(benzylthiocarbamoylamino)-5-chlorobenzene, 1,3-di(benzylthiocarbamoylamino)-4-methoxybenzene, 1,3-di(benzoylthiocarbamoylamino)-2,4,6-trimethylbenzene, 1,4-di(benzylthiocarbamoylamino)benzene, 1,4-di(benzoylthiocarbamoylamino)-2-chlorobenzene, 1,4-di(benzylthiocarbamoylamino)-2-methylbenzene, 1,4-di(benzoylthiocarbamoylamino)-2,5-dimethylbenzene, 1,4-di(benzylthiocarbamoylamino)-2,3,5,6-tetramethylbenzene, 1,4-di(benzoylthiocarbamoylamino)-2-chloro-5-methylbenzene, 4,4-di(benzylthiocarbamoylamino)-3,3'-dimethoxybenzidine, 4,4-di(benzoylthiocarbamoylamino)-3,3'-dimethoxybenzidine, 4,4-di(benzylthiocarbamoylamino)benzidine, 4,4-di(benzylthiocarbamoylamino)-3,3'-dimethylbenzidine, 4,4-di(benzylthiocarbamoylamino)-3,3'-dichlorobenzidine, 4,4-di(benzylthiocarbamoylamino)-3,3'6,6'-tetrachlorobenzidine, 4,4-di(benzoylthiocarbamoylamino)-3,3',6,6'-tetrachlorobenzidine, 1,5-di(benzylthiocarbamoylamino)naphthalene, and 1,5-di(benzoylthiocarbamoylamino)naphthalene. The compounds of Formulae [1] and [2] of the present invention can be produced by using a reaction of monoisothiocyanate compounds and diamines. Specifically, approximately 2 molar equivalents of a monoisothiocyanate is added to 1 mole of a diamine. Usable solvents are those which dissolve diamines and monoisothiocyanates, including aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chloroform, dichloromethane and chlorobenzene; ethers such as diethylether and tetrahydrofuran; nitriles such as acetonitrile and propionitrile; esters such as ethyl acetate; ketones such as acetone and methylethylketone; non-proton donating polar solvents such as dimethylformamide and dimethylsulfoxide; alcohols such as methanol and ethanol; or mixtures thereof. The reaction temperature is 0 to 150°C, preferably 20 to 80°C. Practical examples of the compounds of Formulae [1] and [2] are shown above, which are symmetrical compounds. However, the present invention is not limited to these symmetrical compounds. Asymmetrical compounds are also included within the scope of the formulae [1] and [2]. The dimerized thiourea compound of Formula [1] has two thiourea structures, which can be considered as a compound in which the two thiourea structures are linked by two aromatic compounds. The invention therefore further provides a composition of the invention as defined above wherein the dimerised thiourea derivative is of one of the following formulae [3] and [4]: wherein A 1 denotes CH 2 , (CH 2 ) 2 , S, O, SO 2 , CONH, NH, or C(CF 3 ) 2 , the two substituents R A , which may be the same or different, are each independently selected from a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, and each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , which may be the same or different, are each independently as defined above in Formula [1] ; and wherein A 2 denotes S, O, SO 2 , CONH, NH, or C(CF 3 ) 2 ; the two substituents R B , which may be the same or different, are each a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , which may be the same or different, are each independently as defined above in Formula [1]. Of the thiourea compounds of Formula [3], those of Formulae [5] - [6] are preferred: wherein A 1 denotes CH 2 , (CH 2 ) 2 , S, O, SO 2 , CONH, NH, or C(CF 3 ) 2 ), each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is as defined above in Formula [1], X is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen or hydrogen, and n is an integer from 1 to 3. wherein A 1 denotes CH 2 , (CH 2 ) 2 , S, O, SO 2 , CONH, NH, or C(CF 3 ) 2 , each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is as defined above in Formula [1], X is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen or hydrogen, and n is an integer from 1 to 3. The thiourea compounds of Formula [4] can be broadly classified into the following Formulae [7] - [11] by the group (A 2 ) linking two aromatic rings. wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is as defined above in Formula [1], and X and n are as defined above in Formula [5]. wherein each of R1, R2, R3, R4, R5, R6, R7, and R8 is as defined above in Formula [1], and X and n are as defined above in Formula [5]. wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is as defined above in Formula [1] and X and n are as defined above in Formula [5]. wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is as defined above in Formula [1] and X and n are as defined above in Formula [5]. wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is as defined above in Formula [1] and X and n are as defined above in Formula [51. Some of the above compounds are novel. Accordingly, the invention further provides a dimerised thiourea derivative of one of the Formulae [7], [9], [10] and [11] as defined above. Examples of compounds of Formulae [7] and [8] include the following. On the other hand, the dimerized thiourea compound of Formula [2] has two thiourea structures, which can be considered as a compound in which the thiourea structures are linked by a single aromatic compound. Of dimerized thiourea compounds of Formula [2], the dimerized thiourea compound of Formula [12] is preferred wherein R A is as defined above in Formula [3], and B denotes substituted or unsubstituted benzene ring, naphthalene ring, or biphenyl ring. Of the thiourea compounds of Formula [12], those of Formulae [13] - [14] are more preferable: wherein B is as defined above in Formula [2], and X and n are as defined above in Formula [5]. wherein B is as defined above in Formula [2], and X and n are as defined above in Formula [5]. The copper compound used in the present invention can preferably be at least one copper compound selected from copper compounds of an organic acid of Formula [15], copper bis-acetylacetonate, and copper hydroxide: (Y - Z)mCu wherein Y denotes a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group or a heterocyclic residue, Z is COO, SO 4 , SO 3 , PO 4 , and m is an integer from 1 to 4. Practical examples of the compounds of Formula [15] include, but are not limited to, the following: Copper stearate, copper palmitate, copper oleate, copper behenate, copper laurate, copper caprate, copper caprylate, copper caproate, copper valerate, copper isobutyrate, copper 4-cyclohexylbutyrate, copper butyrate, copper propionate, copper acetate, copper formate, copper benzoate, copper toluate, copper t-butylbenzoate, copper chlorobenzoate, copper dichlorobenzoate, copper trichlorobenzoate, copper bromobenzoate, copper iodobenzoate, copper phenylbenzoate, copper benzoylbenzoate, copper nitrobenzoate, copper aminobenzoate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper pimelate, copper suberate, copper azelaate, copper sebacate, copper citrate, copper phthalate, copper monoalkylester phthalate, copper monoacryloylester phthalate, copper naphthenate, copper naphthalenecarboxylate, copper diphenylamine-2-carboxylate, copper tartarate, copper gluconate, copper octylate, copper benzenesulfonate, copper p-toluenesulfonate, copper 2, 5-dimethylbenzenesulfonate, copper 2-methoxycarbonyl-5-methylsulfonate, copper dodecylbenzenesulfonate, copper naphthalenesulfonate, copper aminonaphthalenesulfonate, copper dodecylsulfate, copper α -naphthylphosphate, copper sterarylphosphate, copper laurylphosphate, copper di-2-ethylhexylphosphate, and copper isodecylphosphate. Each of the above copper compound and the dimerized thiourea derivative alone has no absorption in the near-infrared region (780nm - 2,500nm), or slightly absorbs a specific wavelength, and the absorption in the near-infrared region is not substantially changed even when each of the compound alone is heat treated. Further, a composition comprising a mere mixture of the copper compound and the dimerized thiourea derivative does not provide a substantial change in near-infrared absorption. However, when the composition is heat treated, they immediately react to have a nearly uniform and strong absorption over the entire near-infrared region. Therefore, the composition comprising a mixture of the dimerized thiourea derivative and the copper compound is a superior near-infrared absorbent composition, and a reaction product obtained by heating the composition is a very good near-infrared absorbent. Degree of the near-infrared absorption can be flexibly controlled by adjusting the types and ratio of the dimerized thiourea derivative and the copper compound, heating temperature, heating time, and the like. The ratio of the dimerized thiourea derivative and the copper compound is normally about 8:2 to 1:2 in molar ratio, preferably 2:1 to 1:1, the heating temperature is 100 to 250°C, preferably 120 to 180°C, and a heating time of several milliseconds is sufficient. Various applications can be envisaged which exploit the properties of the composition of the invention. For example, when the near-infrared absorbent composition is provided with heat energy, since the portion provided with the heat energy is changed to near-infrared absorbent but has almost no absorption in the visible region, the composition can be incorporated in a heating pattern or a near-infrared detection apparatus, and an appropriate visualization means is used to obtain the recording image. By using a laser light having a wavelength in the near-infrared region as a heat source, a noncontacting visible image recording system can be obtained. Further, utilizing the property of having a strong absorption over nearly the entire near-infrared region, a near-infrared absorbent molding and a heat wave shielding material can be obtained. The near-infrared absorbent molding can be obtained by melting the dimerized thiourea compound and the copper compound or a composition comprising a mixture thereof with a resin and then molding, or by heat molding a near-infrared absorbent obtained by previously heating the raw materials to above a predetermined temperature with a resin, in the form of granules, films, sheets, boards, or desired three-dimensional shapes. Further, the near-infrared absorbent or the near-infrared absorbent composition can be sprayed, coated, or impregnated to a desired substrate, dried, and heated to endow the substrate with a near-infrared absorbing property. Since near-infrared light acts as a heat source, when a highly transparent resin is used as the resin or the substrate, the material can also be used as a heat wave shielding material which blocks the near-infrared region. The dimerized thiourea compound and the copper compound can be added in amounts of 0.05 to 5% by weight, preferably 0. 1 to 1% by weight, based on the resin to obtain a near-infrared absorbent resin composition which is less colored, good in visible light transmittance, and superior in near-infrared absorbing property. The resin can be known thermoplastic resins such as polyethylene, polyvinylchloride, poly(meth)acrylic acid or poly(meth)acrylic esters, polycarbonate, polystyrene, and styrene-butadiene copolymers; known thermosetting resins such as urea resins, melamine resins, and epoxy resins; and natural resins such as rosin and dammar. Thermoplastic resins are widely used for producing moldings. For example, for glazing applications, polycarbonate, polymethyl methacrylate, and the like are used to good advantage in terms of transparency and strength. In the production of moldings, since the molding temperature depends on the type of resin used, a dimerized thiourea derivative of type that does not decompose at the temperature can be selected to prevent unpleasant gas evolution. In molding, it is preferable that the resin is mixed with the near-infrared absorbent composition of the present invention by a tumbler, mixer, blender, or the like to obtain a master batch and, as needed, additives such as a dye for coloring, a pigment, an antioxidant, a stabilizer such as an ultraviolet absorbent, a fire-retardant agent, a plasticizer, and the like to obtain a compounding material. Further, the near-infrared absorbent resin and its molding can also be obtained by mixing a polymerizable raw material with the dimerized thiourea compound of the present invention and the copper compound, and heat polymerized in the presence of a radical polymerization initiator. The dimerized thiourea derivative and the copper compound are used in total amounts of about 0. 1 to 0.5 parts by weight, preferably 0.2 to 1.0 part by weight, based on 100 parts by weight of the polymerizable raw material to obtain a sufficient effect. The polymerizable raw material is at least one of known radical polymerizable unsaturated monomers such as (meth)acrylic acid, (meth)acrylic esters, styrene, olefins, vinylchloride, and the like, and a prepolymer of these polymerizable monomers dissolved in the polymerizable monomer can also be used as the polymerizable raw material. The polymerizable raw material can be polymerized by known polymerization means to obtain polymers such as poly(meth)acrylic acid, poly(meth)acrylic esters, polyolefins, polyvinylchloride, polyvinylidenechloride, polystyrene, polyesters, polyvinylacetate, polyvinylalcohol, and the like. Radical polymerization is initiated by the action of heat, light, or radiation, and normally carried out in the presence of an initiator or photosensitizer. Further, by the polymerization condition, the process is classified into block polymerization, solution polymerization, emulsion polymerization, and suspension polymerization. Typical examples of the radical polymerization initiator are azo compound type initiators and peroxide type initiators. Practical examples of the azo compound type initiator include 2,2'-azo-bis-isobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azo-bis-1-cyclohexanecarbonitrile, methyl 2,2'-azo-bis-isobutyrate, and the like; and practical examples of the peroxide type initiator include benzoylperoxide, di-1-butylperoxide, diisopropylperoxydicarbonate, dicyclohexylperoxydicarbonate, and the like. In the present invention, when polymerization is carried out using a peroxide type initiator, the near-infrared absorption may be reduced depending on the type and amount of the initiator. Therefore, the use of an azo compound type initiator is preferable. For poly(meth)acrylic acid, poly(meth)acrylic ester, polystyrene, and polyvinylacetate, a molding can be produced simultaneously with block polymerization of each monomer. Further, when two or more types of monomers are combined and block polymerized, a copolymer can be obtained. Further, for polyolefin, polyvinylchloride, polyvinylidenechloride, polycarbonate, polyester, and polyvinylacetate, films can be produced by polymerization of each monomer followed by melt extrusion. For polyvinylchloride, polycarbonate, methacrylic resins, polystyrene, polypropylene, and polyethylene, plates and films can be produced by a solution flow method after polymerization. In photopolymerization, a photopolymerization initiator and, as needed, a visible light sensitizer are added to the above polymerizable raw material, and polymerization is carried out. Practical examples of the photopolymerization initiator include acetophenone, 2,2'-diethoxyacetophenone, benzophenone, 4,4'-bisdimethylaminobenzophenone, benzoin, benzoinethylether, and the like, of which one or more types are used. Polymerization is carried out by a method in which a mixture mainly comprising the above polymerizable raw material, the near-infrared absorbent composition or the near-infrared absorbent of the present invention, and a photopolymerization initiator is coated on a substrate, or sealed in a transparent made of glass, plastics, or the like, and then irradiated with light. Further, an object already formed to a certain shape can also be endowed with a near-infrared absorbent property by spraying, coating, or printing a slurry comprising a composition of the dimerized thiourea derivative of the present invention and the copper compound dissolved or dispersed with a binder on a substrate, followed by drying and heating, or by spraying, coating, or printing a slurry comprising the near-infrared absorbent of the present invention and a binder. Further, the substrate can also be endowed with a near-infrared absorbent property by a method in which a solution of the resin composition containing the near-infrared absorbent composition in a solvent or a molten liquid thereof is coated on the substrate, dried, and heat treated. For example, when the dimerized thiourea derivative and the copper compound are dissolved in a silicone-based hard coating agent, coated on the substrate, and heat treated, polysiloxane condenses to form a glass-like substance, and the dimerized thiourea derivative and the copper compound react to yield a near-infrared absorbent, thereby obtaining a near infrared absorbent glass-like protective coating. The silicone-based hard coating agent mainly comprises three-functional and four-functional organoalkoxysilane monomers, which are hydrolyzed in the presence of a solvent and an acid or base, and partially condensed to obtain a polysiloxane, which is dissolved in a solvent such as alcohol, cellosolve, ketone, or the like, mixed with a curing catalyst and, according to a required function, mixed with various additives to obtain a sol. The sol can be cured at a low temperature of about 120 to 150 0 C by selecting a catalyst, thereby coating a resin having a low heat distortion temperature such as polymethylmethacrylate with a near-infrared absorbent glass-like protective film without deformation of the resin. The total amount of the dimerized thiourea compound and the copper compound is 5 to 50 parts by weight based on 100 parts by weight of solid of the silicone-based hard coating agent, and the molar ratio of the dimerized thiourea derivative and the copper compound is 8:2 to 1:2. Since a plastic sheet or film comprising the near-infrared absorbent contained in a highly transparent plastic has a wide and strong absorption in the near-infrared region, it can be used as a heat wave shielding material. The heat wave shielding plastic sheet is required to have the following quality: (1) it cuts off sunlight energy as much as possible, and allows visible light to pass, (2) physical strength is not reduced, (3) the heat wave shielding effect does not vary with time, and (4) it is clear and less turbid as possible. Heat wave shielding performance of the heat wave shielding material can be evaluated for sunlight transmittance and visible light transmittance according to JIS R 3106. The visible light transmittance represents a visual transmittance to daylight (standard light D 65 ), of which the greater value is the lighter. The sunlight transmittance represents a transmittance to sunlight, that is, radiations of the near-ultraviolet, visible, and near-infrared regions which comes from the sun passing through the atmosphere to the ground, of which the lower the value, the higher is the cutting rate. The sunlight energy distributes in 0.3 to 2.5µm in wavelength. Of the total sunlight energy, that of the visible light region (0.38 to 0.78µm) accounts for about 45%, and the remaining 50% is in the near-infrared region (0.78 to 2.5 µm). When there is no sunlight blocking material, the sunlight transmittance and visible light transmittance are 100. For a shielding material which passes all of near-infrared rays-and cuts off all of visible light (the visible light transmittance is 0), from the wavelength ratio of sunlight, the sunlight transmittance is 55, but it is dark to human eyes. Such a heat wave shielding material is not directed to by the present invention. Further, as the visible light transmittance is increased, the sunlight transmittance of course increases, and the result becomes worse. On the contrary, in an ideal condition where all of visible light is passed (visible light transmittance 100) and all of near-infrared rays are cut off, the sunlight transmittance is 50. Then, since the objective heat wave shielding material is required to pass visible light as much as possible and cut off near-infrared rays as much as possible, in the present invention a heat wave shielding efficiency is defined by Formula [A]: η= [(E-V)/50] x 100 (wherein E is a visible light transmittance, Y is a sunlight transmittance, and 50 indicates a sunlight transmittance of an ideal heat wave shielding material.) That is, in an ideal condition as a heat wave shielding material, η 0 = [(100-50)/50] x 100 = 100 (%), and when all of light is passed, η = [(100-100)/50] x 100 = 0 (%). Therefore, the greater the η value, the better the heat wave shielding efficiency of the plate. When the heat wave shielding material of the present invention which can sufficiently transmits visible light while cutting off near-infrared light is used, sunlight passed through the material feels no heat. The material can be used in summer in the exterior applications for roofing, exterior materials, and the like such as in a carport, sunroom, terrace, and the like to supply bright and cool light, thereby suppressing temperature increase in rooms and reducing operation of air conditioners. Further, the heat wave shielding material of the present invention blocks near-infrared light by absorbing it, finally the absorbed near-infrared light is partly converted to heat, and emits radiation energy according to the temperature of the substance. The radiation energy is 3.0 to 30µm in wavelength. Therefore, when the heat wave shielding material is used in the interiors, a greenhouse effect occurs unless an efficient heat dissipation is effected but, when it is used in winter, operation of heaters can be reduced. Since the heat wave shielding material is required to pass visible light as much as possible, the material resin desirably has a high transparency and, at the same time, it is necessary to select the dimerized thiourea compound and the copper compound which dissolve in the polymerizable raw material. For the copper compound, copper salt of phthalic acid derivative which is readily soluble in the polymerizable raw material as disclosed in Japanese Patent Laid-open Publication 3-246256. The transparent polymer is preferably based on an unsaturated monomer such as (meth)acrylic acid, (meth)acrylic ester, styrene, vinylacetate, or the like as the polymerizable monomer and, particularly, one which is based mainly on (meth)acrylic ester is preferable. The (meth)acrylic ester is a (meth)acrylic ester of a compound having monohydric or polyhydric hyroxyl groups or in which a prepolymer of the (meth)acrylic ester is dissolved. The polymerization condition is not specifically limited but, for example, when the dimerized thiourea compound and the copper compound and a polymerization initiator are dissolved in methylmethacrylate and block polymerized in a mold, an initial-stage polymerization (pre-polymerization) is carried out at 40 to 90°C for 2 to 3 hours, and a post-stage polymerization (main polymerization) is carried out at 90 to 140°C for 2 to 3 hours to obtain a near-infrared absorbent resin plate. It is also a preferable method that a resin material containing the dimerized thiourea compound and the copper compound is mixed with a photopolymerization initiator, and photopolymerized to obtain a near-infrared absorbent plate. The thus obtained heat wave shielding material, for example a 1 mm thick near-infrared absorbent methacrylic sheet obtained by a method in which 100 parts by weight of methacrylic resin is mixed with 0.3 parts by weight of the near-infrared absorbent composition and extrusion injection molded has a sunlight transmittance of 55 to 60% and a visible light transmittance of 70 to 75%. Further, a 2 mm thick near-infrared absorbent methacrylic sheet containing 0.5 parts by weight of the near-infrared absorbent composition has a sunlight transmittance of 15 to 25% and a visible light transmittance of 30 to 40%. At either concentration, the heat wave shielding efficiency is 35 to 45%. Further, the heat wave shielding material can also cut off ultraviolet rays. Since such an ultraviolet shielding material is transparent, that is, passes visible light, it is effectively used in sunglasses, window glass, and the like which can block harmful ultraviolet rays without inconvenience in viewing objects such as in seashore, skiing ground, high mountains, welding place, and the like. The invention is further illustrated in the accompanying drawings which are as follows: Fig. 1 A: A transmission spectrum of a 3. 05 mm thick PMMA plate obtained in Example 37. B: A transmission spectrum of a 3 mm thick PMMA plate. Fig.2 C: A transmission spectrum of a 2 mm thick PS plate obtained in Example 38. D: A transmission spectrum of a 2 mm thick PS plate. Fig.3 E: A transmission spectrum of a 2 mm thick PS plate obtained in Example 39. Fig.4 F: A transmission spectrum of a 1 mm thick PMMA plate obtained in Example 40. G: A transmission spectrum of a 1 mm thick PMMA plate. Fig.5 H: A transmission spectrum of a 2 mm thick PMMA plate obtained in Example 41. I: A transmission spectrum of a 2 mm thick PMMA plate. J: A transmission spectrum of a brown-colored 2 mm thick PMMA plate. Fig.6 K: A transmission spectrum of a 2 mm thick PMMA plate obtained in Example 42. Fig.7 L: A transmission spectrum of a 2 mm thick PMMA plate obtained in Example 43. The present invention will be described further in detail with reference to the embodiments. Example 1 (Synthesis of Compound A-1) 4,4'-di(phenylthiocarbamoylamino)diphenylmethane 4,4'-Diaminodiphenylmethane (0.991g, 5mM) was dissolved in 20 ml of ethyl acetate, and 2 equivalents of phenylisothiocyanate (1.352g, 10mM) was added. The mixture was stirred at 80°C for 10 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 1.79g (75.9% yield) of a a colorless crystal of compound A-1. Melting point: 181°C 1 H-NMR (DMSO-d 6 ) ppm δ = 3.97 (2H, s, -C H 2 -) δ = 7.17-7.55 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 9.02 (4H, broad s, -N H - x 2) Example 2 (Synthesis of Compound A-2) 4,4'-di(benzylthiocarbamoylamino)diphenylmethane 4,4'-Diaminodiphenylmethane (0.991g, 5mM) was dissolved in 20 ml of ethyl acetate, and 2 equivalents of benzylisothiocyanate (1.492g, 10mM) was added. The mixture was stirred at 80°C for 10 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 2.24g (90.2% yield) of a colorless crystal of compond A-2. Melting point: 200°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 3.87 (2H, s,  -C H 2 - ) δ = 4.72 (4H, d, J=5.5,  -C H 2 - ) δ = 7.18-7.36 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 8.11 (2H, broad s, -CH 2 N H - x 2) δ = 9.55 (2H, broad s, -N H - x 2) Example 3 (Synthesis of Compound A-3) 4,4'-di(benzoylthiocarbamoylamino)diphenylmethane 4,4'-Diaminodiphenylmethane (0.496g, 2.5mM) was dissolved in 20 ml of ethyl acetate, and 2 equivalents of benzoylisothiocyanate (0 816g, 5mM) was added. The mixture was stirred at 25°C for 10 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 1.26g (96.1% yield) of a colorless crystal of compound A-3. Melting point: 221°C 1 H-NMR (DMSO-d 6 ) ppm δ = 3.98 (2H, s,  -C H 2 - ) δ = 7.30-7.99 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 11.56 (2H, broad s, -N H - x 2) δ = 12.58 (2H, broad s, -N H - x 2) Example 4 (Synthesis of Compound A-4) 4,4'-di(ethylthiocarbamoylamino)diphenylmethane 4,4'-Diaminodiphenylmethane (0.991g, 5mM) was dissolved in 15 ml of ethyl acetate, and 2 equivalents of ethylisothiocyanate (0.872g, 10mM) was added. The mixture was stirred at 80°C for 30 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 1.21g (64.9% yield) of a colorless crystal of compound A-4. Melting point: 161°C 1 H-NMR (DMSO-d 6 ) ppm δ = 1.09 (3H, t, J=14.3, -C H 3 x 2) δ = 3.46 (2H, t, J=12.6, -C H 2 x 2) δ = 3.86(2H, s,  -C H 2 - ) δ = 7.22 (8H, dd, J=8.4, 8.3, -C 6 H 4 - x 2) δ = 7.67 (2H, broad s, -CH 2 N H - x 2) δ = 9.36 (2H, broad s, -N H - x 2) Example 5 (Synthesis of Compound A-5) 4,4'-di(n-butylthiocarbamoylamino)diphenylmethane 4,4'-Diaminodiphenylmethane (0.991g, 5mM) was dissolved in 15 ml of ethyl acetate, and 2 equivalents of n-butylisothiocyanate (1.152g, 10mM) was added. The mixture was stirred at 80°C for 30 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 1.47g (68.5% yield) of a colorless crystal of compound A-5. Melting point: 174°C 1 H-NMR (DMSO-d 6 ) ppm δ = 0.89 (3H, t, J=14.6, -C H 3 x 2) δ = 1.29 (4H, dd, J=7.1, 7.6, -C H 2 x 2) δ = 1.50 (4H, t, J=14.4, -C H 2 x 2) δ = 3.46 (4H, broad dd, J=5.5, -C H 2 x 2) δ = 3.86 (2H, s,  -C H 2 - ) δ = 7.23 (8H, dd, J=7.6, 7.4, -C 6 H 4 - x 2) δ = 7.67 (2H, broad s, -CH 2 N H x 2) δ = 9.36 (2H, broad s, -N H - x 2) Example 6 (Synthesis of Compound A-6) 4,4'-di(allylthiocarbamoylamino)diphenylmethane 4,4'-Diaminodiphenylmethane (0.991g, 5mM) was dissolved in 15 ml of ethyl acetate, and 2 equivalents of allylisothiocyanate (0.991g, 10mM) was added. The mixture was stirred at 80°C for 60 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 1.01g (51.1% yield) of a colorless crystal of compound A-6. Melting point: 155°C 1 H-NMR (DMSO-d 6 ) ppm δ = 3.87 (2H, s,  -C H 2 - ) δ = 4.12 (4H, collapsed t, CH 2 =CH-C H 2 x 2) δ = 5.07-5.19 (4H, m, CH 2 =CH-C H 2 x 2) δ = 5.83-5.92 (2H, m, CH 2 =CH-C H 2 x 2) δ = 7.23 (8H, dd, J=8.3, 8.3, -C 6 H 4 - x 2) δ = 7.77 (2H, broad s, -CH 2 N H x 2) δ = 9.47 (2H, broad s, -N H - x 2) Example 7 (Synthesis of Compound A-7) 4,4'-di(β-phenylethylthiocarbamoylamino)diphenylmethane 4,4'-Diaminodiphenylmethane (0.496g, 2.5mM) was dissolved in 15 ml of ethyl acetate, and 2 equivalents of ethylisothiocyanate (0.816g, 5mM) was added. The mixture was stirred at 80°C for 30 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 0.50g (38.0% yield) of a colorless crystal of compound A-7. Melting point: 145°C 1 H-NMR (DMSO-d 6 ) ppm δ = 2.85 (3H, t, J=14.3, -C H 3 x 2) δ = 3.69 (2H, t, J=12.6, -C H 2 x 2) δ = 3.87 (2H, s,  -C H 2 - ) δ = 7.08-7.33 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 7.66 (2H, broad s, -CH 2 N H - x 2) δ = 9.49 (2H, broad s, -N H - x 2) Example 8 (Synthesis of Compound A-8) 4,4'-di(ethoxycarbonylthiocarbamoylamino)diphenylmethane 4,4'-Diaminodiphenylmethane (0.496g, 2.5mM) was dissolved in 20 ml of ethyl acetate, and 10 ml of an ethyl acetate solution of 2 equivalents of ethoxycarbonylisothiocyanate (0.816g, 5mM) was added. The mixture was stirred at 80°C for 10 minutes, after cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 1.07g (92.8% yield) of a colorless crystal of compound A-8. Melting point: 172°C 1H-NMR (DMSO-d 6 ) ppm δ = 1.25 (3H, t, J=14.1, -C H 3 x 2) δ = 3.94 (2H, s,  -C H 2 - ) δ = 4.20 (2H, t J=12.6, 0-C H 2 x 2) δ = 7.26, 7.51 (8H, dd, J=8.4, 8.3, -C 6 H 4 - x 2) δ = 11.24 (2H, broad s, -N H - x 2) δ = 11.48 (2H, broad s, -N H - x 2) Example 9 (Synthesis of Compound A-9) 4,4'-di(phenylthiocarbamoylamino)diphenylether 4,4'-Diaminodiphenylether (1.001g, 5mM) was dissolved in 30 ml of acetone, and 2 equivalents of phenylisothiocyanate (1.352g, 10mM) was added. The mixture was stirred at 40°C for 75 minutes, after cooling, the reaction mixture was filtered, and washed with acetone/n-hexane to obtain 1.96g (83.4% yield) of a colorless crystal of compound A-9. Melting point: 201°C 1 H-NMR (DMSO-d 6 ) ppm δ = 6.97-7.48 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 9.76 (2H, broad s, -N H - x 2) Example 10 (Synthesis of Compound A-10) 4,4'-di(benzylthiocarbamoylamino)diphenylether 4,4'-Diaminodiphenylether (1.001g, 5mM) was dissolved in 30 ml of acetone, and 2 equivalents of benzylisothiocyanate (1.492g, 10mM) was added. The mixture was stirred at 55°C for 15 minutes, after cooling, the reaction mixture was filtered, and washed with acetone/n-hexane to obtain 1.19g (47.8% yield) of a colorless crystal of compound A-10. Melting point: 194°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 4.75 (4H, d, J=5.4,  -C H 2 - x 2) δ = 6.97-7.42 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 8.08 (2H, broad s, -CH 2 N H - x 2) δ = 9.54 (2H, broad s, -N H - x 2) Example 11 (Synthesis of Compound A-11) 4,4'-di(benzoylthiocarbamoylamino)diphenylether 4,4'-Diaminodiphenylether (0.501g, 2.5mM) was dissolved in 30 ml of acetone, and 2 equivalents of benzoylisothiocyanate (0.816g, 5mM) was added. The mixture was stirred at 55°C for 15 minutes, after cooling, the reaction mixture was filtered, and washed with acetone/n-hexane to obtain 1.23g (93.2% yield) of a colorless crystal of compound A-11. Melting point: 213°C 1 H-NMR (DMSO-d 6 ) ppm δ = 7.09-8.01 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 11.59 (2H, broad s, -N H - x 2) δ = 12.56 (2H, broad s, -N H - x 2) Example 12 (Synthesis of Compound A-12) 4,4'-di(benzylthiocarbamoylamino)diphenylsulfone 4,4'-Diaminodipheylsulfone (1.242g, 5mM) was dissolvedi n 10 ml of a mixture of acetone and ethyl acetate, and 2 equivalents of benzylisothiocyanate (1.492g, 10mM) was added. The mixture was stirred at 55°C for 90 minutes, after cooling, the reaction mixture was filtered, and washed with acetone/n-hexane to obtain 1.75g (64. 1% yield) of a colorless crystal of compound A-12. Melting point: 203°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 4.74 (4H, d, J=5.2,  -C H 2 - x 2) δ = 7.24-7.88 (18H, m, -C 5 H 4 - x 2, C 6 H 5 - x 2) δ = 8.50 (2H, broad s, -CH 2 N H - x 2) δ = 9.97 (2H, broad s, -N H - x 2) Example 13 (Synthesis of Compound A-13) 4,4'-di(benzoylthiocarbamoylamino)diphenylsulfone 4,4'-Diaminodiphenylsulfone (0.621g, 2.5mM) was dissolved in 10 ml of a mixture of acetone and ethyl acetate, and 2 equivalents of benzoylisothiocyanate (0.816g, 5mM) was added. The mixture was stirred at 55°C for 90 minutes, after cooling, the reaction mixture was filtered, and washed with acetone/n-hexane to obtain 1.30g (90.5% yield) of a colorless crystal of compound A-13. Melting point: 219°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 7.52-8.03 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 11.76 (2H, broad s, -N H - x 2) δ = 12.74 (2H, broad s, -N H - x 2) Example 14 (Synthesis of Compound A-14) 4,4'-di(benzylthiocarbamoylamino)diphenylsulfide 4,4'-Diaminodiphenylsulfide (1.082g, 5mM) was dissolved in 10 ml of ethyl acetate, and 2 equivalents of benzylisothiocyanate (1.492g, 10mM) was added. The mixture was stirred at 55°C for 90 minutes, after cooling, the reaction mixture was filtered, and washed with acetone/n-hexane to obtain 1.00g (77.7% yield) of a colorless crystal of compound A-14. Melting point: 183°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 4.73 (4H, d, J=5.2, -C H 2 - x 2) δ = 7.23-7.49 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 8.27 (2H, broad s, -CH 2 N H - x 2) δ = 9.71 (2H, broad s, -N H - x 2) Example 15 (Synthesis of Compound A-15) 4,4'-di(phenylthiocarbamoylamino)benzanilide 4,4'-di(Diaminobenzanilide (0.658g, 2.5mM) was dissolved in 20 ml of acetone, and 2 equivalents of phenylisothiocyanate (0.676g, 5mM) was added. The mixture was stirred at 55°C for 10 minutes, after cooling, the reaction mixture was filtered, and washed with acetone/n-hexane to obtain 0.90g (72.3% yield) of a colorless crystal of compound A-15. Melting point: 206°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 7.12-7.95 (18H, m, -C 6 H 4 - x 2, C 5 H 5 - x 2) δ = 9.75 (2H, broad s, -N H - x 2) δ = 10.04 (2H, broad s, -N H - x 2) δ = 10.19 (1H, broad s, -N H - ) Example 16 (Synthesis of Compound A-16) 4,4'-di(benzylthiocarbamoylamino)benzanilide 4,4'-Diaminobenzanilide (0.568g , 2.5mM) was dissolved in 20 ml of acetone, and 2 equivalents of benzylisothiocyanate (0.746g, 5mM) was added. The mixture was stirred at 55°C for 10 minutes, after cooling, the reaction mixture was filtered, and washed with acetone/n-hexane to obtain 0.57g (43.4% yield) of a colorless crystal of compound A-16. Melting point: 207°C 1 -HNMR (DMSO-d 6 ) ppm δ = 4.75 (4H, t, J=12. 8,  -C H 2 - x 2) δ = 7.23-7.93 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 8.08 (1H, broad s, -CH 2 N H -) δ = 8.43 (1H, broad s, -CH 2 N H -) δ = 9.56 (1H, broad s, -N H -) δ = 9.91 (1H, broad s, -N H -) δ = 10.17 (1H, s, -N H -) Example 17 (Synthesis of Compound A-17) 4,4'-di(phenylthiocarbamoylamino)diphenylethane 4,4'-Diaminodiphenylethane (0.531g, 2.5mM) was dissolved in 20 ml of ethyl acetate, and 2 equivalents of phenylisothiocyanate (0.676g, 5mM) was added. The mixture was stirred at 40°C for 60 minutes, after cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 0.91g (75.4% yield) of a colorless crystal of compound A-17. Melting point: 198°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 2.86 (4H, s,  -C H 2 -C H 2 -  ) δ = 7.09-7.49 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 9.74 (4H, broad s, -N H - x 2) Example 18 (Synthesis of Compound A-18) 4,4'-di(benzylthiocarbamoylamino)diphenylethane 4,4'-Diaminodiphenylethane (0.531g, 2.5mM) was dissolved in 20 ml of ethyl acetate, and 2 equivalents of benzylisothiocyanate (0.746g, 5mM) was added. The mixture was stirred at 80°C for 60 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 1.11g (86.9% yield) of a colorless crystal of compound A-18. Melting point: 197°C 1 H-NMR (DMSO-d 6 ) ppm δ = 2.84 (4H, s,  -C H 2 -C H 2 - ) δ = 4.73 (4H, d, J=5.2,  -C H 2 - x 2) δ = 7.19-7.34 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 8.10 (2H, broad s, -CH 2 N H - x 2) δ = 9.55 (2H, broad s, -N H - x 2) Example 19 (Synthesis of Compound A-19) 4,4'-di(benzylthiocarbamoylamino)-3,3'-dimethyldiphenylmethane 4,4'-Diamino-3,3'-dimethyldiphenylmethane (0.566g, 2.5mM) was dissolved in 10 ml of ethyl acetate, and 2 equivalents of benzylisothiocyanate (0.746g, 5mM) was added. The mixture was stirred at 80°C for 10 minutes, after cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 1.00g (77.7% yield) of a pale pink crystal of compound A-19. Melting point: 187°C 1 H-NMR (DMSO-d 6 ) ppm δ = 2.12 (6H, s,  -C H 3 x 2) δ = 3.83 (2H, s,  -C H 2 - ) δ = 4.68 (4H, d, J=5.0,  -C H 2 - x 2) δ = 7.06-7.34 (16H, m, -C 6 H 3 - x 2, C 6 H 5 - x 2) δ = 7.84 (2H, broad s, -CH 2 N H - x 2) δ = 9.12 (2H, broad s, -N H - x 2) Example 20 (Synthesis of Compound A-20) 4,4'-di(benzoylthiocarbamoylamino)-3,3'-dimethyldiphenylmethane 4, 4'-Diamino-3,3' -dimethyldiphenylmethane (0.566g, 2.5mM) was dissolved in 10 ml of ethyl acetate, and 2 equivalents of benzoylisothiocyanate (0.816g, 5mM) was added. The mixture was stirred at 80°C for 10 minutes, after cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 1.24g (89.7% yield) of a pale pink crystal of compound A-20. Melting point: 220°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 2.24 (6H, s,  -C H 3 x 2) δ = 3.92 (2H, s,  -C H 2 - ) δ = 7.14-8.01 (16H, m, -C 6 H 3 - x 2, C 6 H 5 - x 2) δ = 11.60 (2H, broad s, -N H - x 2) δ = 12.23 (2H, broad s, -N H - x 2) Example 21 (Synthesis of Compound A-21) 4,4'-di(benzylthiocarbamoylamino)diphenylamine 4,4'-Diaminodiphenylamine sulfate (1.486g, 5mM) was dissolved in 100 ml of water, sodium hydroxide (0.40g, 10mM) was added and stirred, and extracted with 150 ml of ethyl acetate. The resulting ethyl acetate solution was thoroughly washed with water, dewatered, and vacuum concentrated to about 20 ml. Precipitated insoluble substances were filtered out, and 2 equivalents of benzylisothiocyanate (1.492g, 10mM) was added to the filtrate. The mixture was stirred at 80°C for 30 minutes, after cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 0.97g (39.0% yield) of a pale pink crystal of compound A-21. Melting point: 179°C 1 H-NMR (DMSO-d 6 ) ppm δ = 4.72 (4H, d, J=5.6, -C H 2 - x 2) δ = 7.01-7.33 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 7.93 (2H, broad s, -CH 2 N H - x 2) δ = 8.20 (1H, broad s, -N H -) δ = 9.42 (2H, s, -N H - x 2) Example 22 (Synthesis of Compound A-22) 4, 4' -di(benzoylthiocarbamoylamino)diphenylamine 4,4'-Diaminodiphenylamine sulfate (1.486g, 5mM) was dissolved in 100 ml of water, sodium hydroxide (0.40g, 10mM) was added and stirred, and extracted with 150 ml of ethyl acetate. The resulting ethyl acetate solution was thoroughly washed with water, dewatered, and vacuum concentrated to about 20 ml. Precipitated insoluble substances were filtered out, and an ethyl acetate solution of 2 equivalents of benzoylisothiocyanate (1.492g, 10mM) was added to the filtrate. The mixture was stirred at room temperature for 30 minutes, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 1.60g (51.1% yield) of a light brown crystal of compound A-22. Melting point: 210°C 1 H-NMR (DMSO-d 6 ) ppm δ = 7.12-8.00 (18H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 8.47 (1H, s, -N H -) δ = 11.50 (2H, s, -N H - x 2) δ = 12.53 (2H, s, -N H - x 2) Example 23 (Synthesis of Compound A-23) 4,4'-di(benzoylthiocarbamoylamino)-diphenylhexafluoropropane 4,4'-Diaminodiphenylhexafluoropropane (0.363g, 1mM) was dissolved in 20 ml of ethyl acetate, and 2 equivalents of benzoylisothiocyanate (0.326g, 2mM) was added. The mixture was stirred at 80°C for 60 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 0.671g (97.3% yield) of a colorless crystal of compound A-23. Melting point: 206°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 7.41-8.01 (16H, m, -C 6 H 3 - x 2, C 6 H 5 - x 2) δ = 11.67 (2H, broad s, -N H - x 2) δ = 12.73 (2H, broad s, -N H - x 2) Example 24 (Synthesis of Compound A-24) 1,3-di(benzylthiocarbamoylamino)benzene m-Phenylenediamine (0.541g, 5mM) was dissolved in 20 ml of ethyl acetate, and 2 equivalents of benzylisothiocyanate (1.492g, 10mM) was added. The mixture was stirred at 80°C for 10 minutes, after cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 1.90g (93.5% yield) of a white crystal of 1,3-dibenzylthiocarbamoylaminobenzene. Melting point: 152°C 1HNMR (Acetone-d 6 ) ppm δ = 4.87 (4H, d, J=5.6,  -C H 2 x 2) δ = 7.16-7.40 (14H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 7.73 (2H, broad t, -CH 2 N H - x 2) δ = 9.04 (4H, broad s, -N H - x 2) Example 25 (Synthesis of Compound A-25) 1,4-di(benzylthiocarbamoylamino)benzene p-Phenylenediamine (2.707g, 25mM) was dissolved in 20 ml of ethyl acetate, and 2 equivalents of benzylisothiocyanate (7.461g, 50mM) was added. The mixture was stirred at 80°C for 30 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 6.26g (61.6% yield) of a colorless crystal of compound A-25. Melting point: 198°C 1 H-NMR (DMSO-d 6 ) ppm δ = 4.73 (4H, d, J=5.2,  -C H 2 x 2) δ = 7.25-7.38 (14H, m, -C 6 H 4 - x 2, C 6 H 5 - x 2) δ = 8.11 (2H, broad s, -CH 2 N H - x 2) δ = 9.59 (2H, broad s, -N H - x 2) Example 26 (Synthesis of Compound A-26) 1,4-di(benzoylthiocarbamoylamino)-2,5-dimethylbenzene 2,5-Dimethyl-p-phenylenediamine (0.340g, 2.5mM) was dissolved in 30 ml of ethyl acetate, and 2 equivalents of benzoylisothiocyanate (0.816g, 5mM) was added. The mixture was stirred at room temperature for 10 minutes, after cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 1.14g (98.6% yield) of a colorless crystal of compound A-26. Melting point: 228°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 2.26 (6H, s,  -C H 3 x 2) δ = 7.53-7.70 (12H, m, -C 6 H 2 -, C 6 H 5 - x 2) δ = 11.69 (2H, broad s, -N H - x 2) δ = 12.28 (2H, broad s, -N H - x 2) Example 27 (Synthesis of Compound A-27) 4,4'-di(benzoylthiocarbamoylamino)-3,3'-dimethoxybenzidine o-Anisidine (0.611g, 2.5mM) was dissolved in 30 ml of ethyl acetate, and 2 equivalents of benzoylisothiocyanate (0.816g, 5mM) was added. The mixture was stirred at room temperature for 10 minutes, after cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 1.18g (82.7% yield) of a colorless crystal of compound A-27. Melting point: 250°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 4.02 (6H, s,  -C H 3 x 2) δ = 7.37-8.73 (16H, m, -C 6 H 3 - x 2, C 6 H 5 - x 2) δ = 11.51 (2H, broad s, -N H - x 2) δ = 13.11 (2H, broad s, -N H - x 2) Example 28 (Synthesis of Compound A-28) 4,4'-di(benzoylthiocarbamoylamino)-3,3' dichlorobenzidine o-Dichlorobenzidine (0.633g, 2.5mM) was dissolved in 30 ml of ethyl acetate, and 2 equivalents of benzoylisothiocyanate (0.816g, 5mM) was added. The mixture was stirred at room temperature for 10 minutes, after cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 1.44g (99.6% yield) of a pale yellow crystal of compound A-28. Melting point: 225°C (dec.) 1 H-NMR (DMSO-d 6 ) ppm δ = 7.54-8.30 (16H, m, -C 6 H 3 - x 2, C 6 H 5 - x 2) δ = 11.91 (2H, broad s, -N H - x 2) δ = 12.83 (2H, broad s, -N H - x 2) Example 29 (Synthesis of Compound A-29) 1,5-di(benzylthiocarbamoylamino)naphthalene 1,5-Naphthalenediamine (0.791g, 5mM) was dissolved in 20 ml of ethyl acetate, and 2 equivalents of benzylisothiocyanate (1.492g, 10mM) was added. The mixture was stirred at 80°C for 30 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 0.70g (30.7% yield) of a colorless crystal of compound A-29. Melting point: 176°C 1 H-NMR (DMSO-d 6 ) ppm δ = 4.70 (4H, d, J=5.8,  -C H 2 x 2) δ = 7.03-7.56 (16H, m, -C 10 H 6 - x 2, C 6 H 5 - x 2) δ = 7.82 (2H, broad s, -CH 2 N H - x 2) δ = 9.57 (2H, s, -N H - x 2) Example 30 (Synthesis of Compound A-30) 4,4'-di(phenylthiocarbamoylamino)diphenylsulfide 4,4'-Diaminodiphenylsulfide (1.082g, 5mM) was dissolved in 10 ml of ethyl acetate, and 2 equivalents of phenylisothiocyanate (1.351g, 10mM) was added. The mixture was stirred at 55°C for 90 minutes, after cooling, the reaction mixture was filtered, and washed with ethylacetate/ n-hexane to obtain 1.10g (45.2% yield) of a colorless crystal of compound A-30. Melting point: 167°C 1 H-NMR (DMSO-d 6 ) ppm δ = 7.13 (2H, t, J=8.0) δ = 7.29 (4H, t, J=8.0) δ = 7.33 (4H, t, J=8.0) δ = 7.47 (4H, t, J=8.0) δ = 7.52 (4H, t, J=8.0) δ = 9.89 (4H, broad s, -N H - x 4) Example 31 (Synthesis of Compound A-31) 4,4'-di(chlorophenylthiocarbamoylamino)diphenylsulfide 4,4'-Diaminodiphenylsulfide (1.082g, 5mM) was dissolved in 10 ml of ethyl acetate, and 2 equivalents of p-chlorophenylisothiocyanate (1.696g, 10mM) was added. The mixture was stirred at 55°C for 90 minutes, after cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 1.39g (50.2% yield) of a colorless crystal of compound A-31. Melting point: 193°C 1 H-NMR (DMSO-d 6 ) ppm δ = 7.30 (4H, d, J=8.0) δ = 7.38 (4H, d, J=8.0) δ = 7.50 (4H, d, J=8.0) δ = 9.95 (4H, broad s, -N H - x 4) Example 32 Thermal analysis of the dimerized thiourea derivatives in Examples 1 to 29 was carried out in air flow to determine decomposition temperatures of the compounds from thermal changes in weight from room temperature to 400°C. Comparing with decomposition temperatures of conventional thiourea compounds of Comparative Examples 1 to 3, the results are shown in Table 1. Decomposition temperatures of dimerized thiourea derivatives Decomposition temperature (°C) Decomposition temperature (°C) Example 1 183.4 Example 16 211.1 2 210.5 17 198.0 3 223.7 18 204.7 4 200.3 19 220.1 5 184.8 20 219.9 6 183.7 21 233.6 7 210.1 22 213.3 8 189.0 23 206.3 9 201.6 24 203.8 10 206.5 25 199.2 11 218.5 26 227.7 12 203.1 27 250.0 13 219.3 28 225.0 14 183.5 29 211.8 15 206.2 Comparative Example 1 1,3-Diphenylthiourea 153.2 2 1,3-Di-o-chlorophenylthiourea 150.5 3 1,3-Di-o-tolylthiourea 152.0 The individual thiourea compounds shown in Comparative Examples decomposed at 150 to 155°C, whereas the decomposition temperatures of the compounds shown in Examples 1 to 29 were above 180°C. A dimerized thiourea compound, which is the most heat-resistant, decomposed at 250°C. Example 33 A composition comprising compound A-2 and copper steara te, mixed in a molar ratio of 2:1, was dry blended in an amo unt of 0.25 parts by weight with 100 parts by weight of poly styrene (PS, Nippon Steel Chemical ESTYRENE), and kneaded by an extruder at an extrusion temperature of 190°C to produce a near-infrared absorbent PS pellet. During the kneading, types and amountsof evolving gases were determined using a g as detection tube. Example 34 A composition comprising compound A-10 and copper stear ate, mixed in a molar ratio of 3:1, was dry blended in an am ount of 0.5 parts by weight with 100 parts by weight of poly styrene (PS, Nippon Steel Chemical ESTYRENE), and kneaded by an extruder at an extrusion temperature of 190°C to produce a near-infrared absorbent PS pellet. During the kneading, types and amounts of evolving gases were determined using a gas detection tube. Example 35 A composition comprising compound A-12 and copper stearate, mixed in a molar ratio of 3:1, was dry blended in an amount of 0.4 parts by weight with 100 parts by weight of polymethylmethacrylate (PMMA, Sumitomo Chemical SUMIPEX), and kneaded by an extruder at an extrusion temperature of 200°C toproduce a near-infrared absorbent PMMA pellet. During the kneading, types and amounts of evolving gases were determined using a gas detection tube. Example 36 A composition comprising compound A-24 and copper β-acryloyloxypropylhydrogenphthalate, mixed in a molar ratio of 4:1, was dry blended in an amount of 0.3 parts by weight with 100 parts by weight of polymethylmethacrylate (PMMA, Sumitomo Chemical SUMIPEX), and kneaded by an extruder at an extrusion temperature of 200°C to produce a near-infrared absorbent PMMA pellet. During the kneading, types and amounts of evolving gases were determined using a gas detection tube. Comparative Example 1 A composition comprising 1,3-diphenylthiourea and copper stearate, mixed in a molar ratio of 5:1, was dry blended in an amount of 0.5 parts by weight with 100 parts by weight of polystyrene (PS, Nippon Steel Chemical ESTYRENE), and kneaded by an extruder at an extrusion temperature of 190°C to produce a near-infrared absorbent PS pellet. During the kneading, types and amounts of evolving gases were determined using a gas detection tube. Comparative Example 2 A composition comprising 1,3-di-tolylthiourea and copper monobutylphthalate, mixed in a molar ratio of 3:1, was dry blended in an amount of 0.3 parts by weight with 100 parts by weight of polymethylmethacrylate (PMMA, Sumitomo Chemical SUMIPEX), and kneaded by an extruder at an extrusion temperature of 200°C to produce a near-infrared absorbent PMMA pellet. During the kneading, types and amounts of evolving gases were determined using a gas detection tube. Evaluation results of Examples 33 to 36 and Comparative Examples 1 and 2 are shown in Table 2. Types and amounts of gases generated in kneading Amine compound Hydrogen sulfide Benzene compound Example 33 <2 ppm 0 ppm <3 ppm Example 34 <1 ppm 0 ppm <3 ppm Example 35 <2 ppm 0 ppm <3 ppm Example 36 <2 ppm 0 ppm <3 ppm Comparative Example 1 7 ppm 50 ppm >60 ppm Comparative Example 2 10 ppm 60 ppm >60 ppm As can be seen from Table 2, when molding is carried out using the near-infrared absorbent compositions according to the present invention, in effect no generation of malodorous gases was noted. Example 37 A composition comprising compound A-23 and copper β-acryloyloxypropylhydrogenphthalate, mixed in a molar ratio of 1:1, was added in an amount of 0.3 parts by weight to 100 parts by weight of methylmethacrylate to dissolve. The solution was mixed with 0.15 parts of 2,2'-azo-bis-isobutyronitrile as a polymerization catalyst, injected into a mold comprising a gasket inserted between two parallel glass plates, immersed in a water bath at 60°C for 3 hours, then heated in an air oven at 90°C to complete polymerization, after cooling, removed from the glass plates to obtain a 3.05 mm thick resin plate. The resulting resin plate was measured for transmission spectrum at 240 nm to 2, 500 nm in wavelength by means of a recording spectrophotometer (Shimadzu UV-3100 and a multipurpose large-sized sample chamber MPC-3100 incorporated with an integration sphere). The result is shown as A in Fig. 1. For comparison, B in the same Figure is a transmission spectrum of a 3 mm thick ordinary methacrylic resin plate (Sumitomo Chemical). As can be seen from comparison of A and B in the Figure, the resin plate containing the near-infrared absorbent of the present invention well passes light of the visible region, and is superior in absorption properties which cannot be obtained with conventional methacrylic resin. Example 38 The near-infrared absorbent PS pellet prepared in Example 33 was injection molded at an injection molding temperature of 160°C to produce a 2 mm thick near-infrared absorbent PS plate. As in Example 35, this near-infrared absorbent PS plate and a 2 mm thick ordinary PS plate not containing a near-infrared absorbent were measured for transmission spectra at 240 nm to 2, 500 nm in wavelength. The results are shown as C and D in Fig.2. As can be seen from comparison of spectra C and D, the inventive well passes light of the visible region, and is superior in absorption properties which cannot be obtained with conventional styrene resin. Example 39 The near-infrared absorbent PS pellet prepared in Example 34 was injection molded at an injection molding temperature of 160°C to produce a 2 mm thick near-infrared absorbent PS plate. As in Example 38, the plate was measured for transmission spectrum. Example 40 The near-infrared absorbent PMMA pellet prepared in Example 35 was injection molded at an injection molding temperature of 190°C to produce a 2 mm thick near-infrared absorbent PMMA plate. As in Example 38, the plate was measured for transmission spectrum. Example 41 The near-infrared absorbent PMMA pellet prepared in Example 36 was injection molded at an injection molding temperature of 190°C to produce a 2 mm thick near-infrared absorbent PMMA plate. As in Example 38, the 2 mm thick plate was measured for transmission spectrum. Example 42 A composition comprising compound A-21 and copper stearate, mixed in a molar ratio of 1:1, was dry blended in an amount of 0.1 part by weight with 100 parts by weight of polymethylmethacrylate (PMMA, Sumitomo Chemical SUMIPEX), an d kneaded by an extruder at an extrusion temperature of 200°C to produce a near-infrared absorbent PMMA pellet. Further, the pellet was injection molded at an injection molding temperature of 190°C to produce a 2 mm thick near-infrared absorbent PMMA plate. As in Example 38, the plate was measured for transmission spectrum. Example 43 A composition comprising compoud A-28 and copper stearate, mixed in a molar ratio of 2:1, was dry blended in an amount of 1 part by weight with 100 parts by weight of polymethylmethacrylate (PMMA, Sumitomo Chemical SUMIPEX), and kneaded by an extruder at an extrusion temperature of 200°C to produce a near-infrared absorbent PMMA pellet. Further, the pellet was injection molded at an injection molding temperature of 190°C to produce a 2 mm thick near-infrared absorbent PMMA plate. As in Example 38, the plate was measured for transmission spectrum. Comparative Example 3 A polystyrene (PS, Nippon Steel Chemical ESTYRENE) pellet was injection molded at an injection molding temperature of 1600C to produce a 2 mm thick PS plate. As in Example 36, the plate was measured for transmission spectrum. Comparative Example 4 A polymethylmethacrylate (PMMA, Sumitomo Chemical SUMIPEX) bead was kneaded by an extruder at a temperature of 200°C to produce a pellet. The PMMA pellet was injection molded at an injection molding temperature of 190°C to produce a 2 mm thick PMMA plate. As in Example 36, the plate was measured for transmission spectrum. comparative Example 5 A commercial brown-colored smoke type polymethylmethacrylate plate was measured for transmission spectrum as in Example 36. From transmission spectra measured in Examples 38 to 43 and Comparative Examples 3 to 5, sunlight transmittances and visible light transmittances were calculated by a method specified in JIS R 3106, and heat wave shielding efficiencies were determined according to Formula [A]. The results are shown in Table 3. Sunlight transmittance, visible light transmittance, and heat wave shielding efficiency of plate Amount (part) Sunlight transmittance I Visible light transmittance E Heat wave shielding efficiency η Ex. 38 0.25 31.385 48.912 35.05 Ex. 39 0.5 18.126 37.285 38.32 Ex. 40 0.3 39.026 60.069 42.09 Ex. 41 0.4 16.120 34.822 37.40 Ex. 42 0.15 35.581 57.516 43.87 Ex. 43 0.75 17.870 36.851 37.96 Comp. Ex.3 - 86.338 89.805 6.93 Comp. Ex.4 - 88.696 92.011 6.63 Comp. Ex.5 - 66.232 39.270 -53.92 As can be seen from Table 3, the plate containing the near-infrared absorbent comprising the dimerized thiourea derivative of the present invention and the copper compound showed a heat wave shielding efficiency of about 40%, whereas that containing no near-infrared absorbent had a heat wave shielding efficiency of only about 5%. Further, the commercial heat wave shielding plate had a heat wave shielding efficiency of -53%. As can be seen from the transmission spectra in Fig.5, the brown-colored plate, which does not absorb near-infrared rays of over 800 nm, merely absorbs visible light to reduce the visible light transmittance, thereby reducing the sunlight transmittance as a whole. Therefore, the heat wave shielding efficiency is a negative value. Thus, the heat wave shielding material using the near-infrared absorbent of the present invention is much superior. A near-infrared absorbent property appears by mixing and heating a thiourea compound and a copper compound, however, since the dimerized thiourea derivative of the present invention is higher in thermal decomposition temperature than conventional thiourea compounds, it does not decompose when the near-infrared absorbent composition comprising the dimerized thiourea derivative and the copper compound is kneaded with a resin, thereby suppressing generation of malodorous gases. As described above, the heat wave shielding material formed by mixing the near-infrared absorbent composition with a transparent resin and molding can be used for roofing, window materials, and the like of carport, sunroom, and terrace to suppress temperature increase in the room. Further, the heat wave shielding material of the present invention passes visible light relatively well and absorbs near-infrared rays in a wide range, and it can also efficiently absorb ultraviolet light as well.

Claims: A composition comprising a copper compound and a dimerized thiourea derivative of Formula [1]: wherein A denotes CH 2 , (CH 2 ) 2 , S, O, SO 2 , CONH, NH, or C(CF 3 ) 2 ; the two substituents R, which may be the same or different, are each independently selected from a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 18 carbons atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms; and each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , which may be the same or different, is independently selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a halogen and hydrogen; the molar ratio of dimerized thiourea derivative to copper compound being from 8:2 to 1:2. A composition comprising a copper compound and a dimerized thiourea derivative of Formula [2] wherein the two substituents R, which may be the same or different, are each independently selected from a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 18 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms; and B denotes substituted or unsubstituted benzene ring, a naphthalene ring, or a biphenyl ring; the molar ratio of dimerized thiourea derivative to copper compound being from 8:2 to 1:2. A composition as defined in claim 1 wherein the dimerized thiourea derivative has one of the following formulae [3] and [4]: (a) wherein A 1 denotes CH 2 (CH 2 ) 2 , S, O, SO 2 , CONH, NH, or C(CF 3 ) 2 , the two substituents R A , which may be the same or different, are each independently selected from a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 18 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, and each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , which may be the same or different, is independently selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a halogen and hydrogen; and (b) wherein A 2 denotes S, O, SO 2 , CONH, NH, or C(CF 3 ) 2 ; the two substituents R B , which may be the same or different, are each a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 which may be the same or different, is independently selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a halogen and hydrogen. A dimerized thiourea derivative of one of the following formulae [7], [9], [10] and [11]: wherein each of R 1, R 2, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is as defined in claim 1, X is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen or hydrogen, and n is an integer of 1 to 3. A dimerized thiourea derivative which is 1,3-di(benzylthiocarbamoylamino)benzene, 1,4-di(benzylthiocarbamoylamino)benzene, 1,4-di(benzoylthiocarbamoylamino)-2,5-dimethyl benzene, 4,4'-di(benzoylthiocarbamoylamino)-3,3'-dimethoxybenzidine, 4,4'-di(benzoylthiocarbamoylamino)-3,3'-dichlorobenzidine or 1,5-di(benzylthiooarbamoylamino) napthalene. A near-infrared absorbent composition obtainable by heating a composition as claimed in claim 1, 2 or 3. A resin composition comprising 0.05 to 5 parts by weight of a composition as claimed in any one of claims 1, 2, 3 and 6 and 100 parts by weight of a resin. A resin composition according to claim 7, wherein the resin is a (meth)acrylic ester resin. A near-infrared absorbent hard-coating agent comprising 5 to 50 parts by weight of a composition as claimed in any one of claims 1, 2, 3 and 6 and 100 parts by weight, as solid, of a silicone type hard-coating agent. A heat wave shielding material obtainable by heat molding a resin composition as claimed in claim 7 or claim 8. A heat wave shielding material which comprises a transparent substrate and, provided on the surface thereof, a coating layer comprising a composition as claimed in claim 7 or claim 8, or a near-infrared absorbent hard-coating agent as claimed in claim 9. A process for preparing a near-infrared absorbent resin composition or a near-infrared absorbent molding, the process comprising mixing 0.1 to 1.5 parts by weight of a composition as claimed in claim 1, 2 or 3 with 100 parts by weight of a polymerizable raw material, and heat polymerizing the resulting mixture in the presence of an azo type radical polymerization initiator. A method according to claim 12, wherein the polymerizable raw material is an unsaturated monomer comprising a (meth)acrylic ester monomer with or without its polymer.

Inventors: HAYASAKA HIDEKI, SATAKE TOSHIMI, TAKANO TOSHIYUKI, HAYASAKA, HIDEKI, SATAKE, TOSHIMI, TAKANO, TOSHIYUKI, HAYASAKA, HIDEKI, C/O NIPPON PAPER IND. CO., LTD., SATAKE, TOSHIMI, C/O NIPPON PAPER IND. CO., LTD., TAKANO, TOSHIYUKI, C/O NIPPON PAPER IND. CO., LTD.
Applicants: JUJO PAPER CO LTD, NIPPON PAPER INDUSTRIES CO., LTD.
Application year: 1994
Main classification: C07C335
IPC codes: C07C335, C08K5, C09K3, C08F2